Method for tuning a deposition rate during an atomic layer deposition process

ABSTRACT

Embodiments of the invention provide methods for depositing a material on a substrate within a processing chamber during a vapor deposition process, such as an atomic layer deposition (ALD) process. In one embodiment, a method is provided which includes sequentially exposing the substrate to a first precursor gas and at least a second precursor gas while depositing a material on the substrate during the ALD process, and continuously or periodically exposing the substrate to a treatment gas prior to and/or during the ALD process. The deposition rate of the material being deposited may be controlled by varying the amount of treatment gas exposed to the substrate. In one example, tantalum nitride is deposited on the substrate and the alkylamino metal precursor gas contains a tantalum precursor, such as pentakis(dimethylamino) tantalum (PDMAT), the second precursor gas contains a nitrogen precursor, such as ammonia, and the treatment gas contains dimethylamine (DMA).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 12/206,705(APPM/12256), filed Sep. 8, 2008, which is herein incorporated byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the invention generally relate to semiconductor and otherelectronic device processing, and more particularly, to an improvedmethod for depositing a material on a substrate during a vapordeposition process.

2. Description of the Related Art

The electronic device industry and the semiconductor industry continueto strive for larger production yields while increasing the uniformityof layers deposited on substrates having increasingly larger surfaceareas. These same factors in combination with new materials also providehigher integration of circuits per unit area on the substrate. The needfor greater deposition rate and process control regarding layercharacteristics rises as the desire for an increased circuitintegration.

Tantalum-containing layers, such as tantalum, tantalum nitride, andtantalum silicon nitride, are often used in multi-level integratedcircuits and pose many challenges to process control, particularly withrespect to contact formation. Barrier layers formed from sputteredtantalum or reactive sputtered tantalum nitride have demonstratedproperties suitable for use to control copper diffusion. Exemplaryproperties include high conductivity, high thermal stability, andresistance to diffusion of foreign atoms.

Both physical vapor deposition (PVD) and atomic layer deposition (ALD)processes are used to deposit tantalum-containing layers in features ofsmall size (e.g., about 90 nm wide) and high aspect ratios of about 5:1.However, it is believed that PVD processes may have reached a limit atthis size and aspect ratio, while ALD processes suffer other problems.Common problems encountered during ALD processes include the lack ofstability for the deposition rate and minumium control for the thicknessof each deposited layer.

An ALD process generally contains a multiplicity of cycles, such that asubstrate surface is sequentially exposed to two or more reagents orprecursors during each ALD cycle while forming the deposited layer. Thethickness of a deposited material is the product of the number ofconducted ALD cycles by the thickness of each deposited layer. Thedeposition rate may be used to adjust the thickness of the depositedmaterial. The deposition rate of each ALD cycle is usually controlled bythe chemical nature of the particular process. Therefore, the depositionrate may be adjusted by controlling certain process conditions, such asthe delivery rate of the gaseous reagent or precursor, modifying theexposure time during the ALD cycle, or adjusting the temperature of theprocess or precursor. However, the deposited material is usuallynon-uniformly formed on the substrate surface while adjusting thedeposition rate by varying these process conditions.

Therefore, there is a need for increasing the stability of thedeposition rate of a deposited layer while controlling the layerthickness during a vapor deposition process.

SUMMARY OF THE INVENTION

Embodiments of the invention provide methods for depositing a materialon a substrate within a processing chamber during a vapor depositionprocess, such as an atomic layer deposition (ALD) process. Generally,the substrate may be continuously or periodically exposed to a treatmentgas containing a reagent prior to and/or during the vapor depositionprocess. The deposition rate of the material being deposited may becontrolled by varying the amount of treatment gas exposed to thesubstrate. Therefore, the deposition rate may be adjusted, such aswithin a range from about 0.05 Å/cycle (Å per ALD cycle) to about 1.0Å/cycle, for example, about 0.5 Å/cycle. In one example, the substratemay be exposed to the treatment gas to reduce the deposition rate of thematerial during the ALD process by about 95% or less.

In one embodiment, a method for depositing a material on a substratesurface is provided which includes exposing a substrate sequentially toan alkylamino metal precursor gas and a second precursor gas whiledepositing a material on the substrate during an ALD process, andexposing the substrate to a treatment gas containing an alkylaminecompound prior to or during the ALD process. In one example, thedeposited material contains tantalum nitride, the alkylamino metalprecursor gas contains a tantalum precursor, such aspentakis(dimethylamino) tantalum (PDMAT), the second precursor gascontains a nitrogen precursor, such as ammonia, and the treatment gascontains methylamine or dimethylamine (DMA).

In another embodiment, a method for depositing a material on a substratesurface is provided which includes exposing a substrate sequentially toan alkylamino metal precursor gas and a second precursor gas whiledepositing a material on the substrate at a first deposition rate duringan ALD process within a processing chamber, exposing the substrate to atreatment gas containing an alkylamine compound, and depositing thematerial on the substrate at a second deposition rate during the ALDprocess, wherein the second deposition rate is less than the firstdeposition rate.

The material may be deposited on the substrate in the absence of thetreatment gas at a first deposition rate during the ALD process and inthe presence of the treatment gas at a second deposition rate during theALD process. The second deposition rate may be about 95% or less of thefirst deposition rate. In other examples, the second deposition rate maybe about 90% or less, about 80% or less, about 70% or less, or about 50%or less of the first deposition rate. In another example, the seconddeposition rate may be within a range from about 0.05 Å/cycle to about1.0 Å/cycle, such as about 0.5 Å/cycle.

In another embodiment, a method for depositing a material on a substratesurface is provided which includes exposing a substrate disposed withinthe processing chamber to a carrier gas having a continuous flow, andexposing the substrate sequentially to a tantalum precursor gas and anitrogen precursor gas while depositing a tantalum nitride material onthe substrate during an ALD process, wherein the tantalum precursor gascontains PDMAT. The ALD process further provides sequentially pulsingthe tantalum precursor gas and the nitrogen precursor gas into thecarrier gas with the continuous flow to deposit the tantalum nitridematerial, and introducing a treatment gas containing dimethylamine tothe carrier gas to expose the substrate to the treatment gas prior toand/or during the ALD process.

In some embodiments, the method for depositing a material on a substratesurface is provided which includes sequentially or simultaneouslyexposing the substrate to a first precursor gas and at least a secondprecursor gas while depositing a material on the substrate during avapor deposition process, and continuously or periodically exposing thesubstrate to a treatment gas containing a reagent prior to and/or duringthe vapor deposition process.

Embodiments provide that the substrate may be sequentially orsimultaneously exposed to the first precursor and at least a secondprecursor gas during the vapor deposition process, such as an ALDprocess or a CVD process. Embodiments also provide that the substratemay be continuously or periodically exposed to the treatment gas priorto and/or during the vapor deposition process. In one embodiment, thevapor deposition process further includes sequentially exposing thesubstrate to the first precursor gas and a second precursor gas duringan ALD process. In one example, the substrate may be continuouslyexposed to the treatment gas during the ALD process. In another example,the substrate may be periodically exposed to the treatment gas duringthe ALD process. In another example, the substrate may be exposed to thetreatment gas prior to the ALD process. In another embodiment, the vapordeposition process further includes simultaneously exposing thesubstrate to the first precursor gas and a second precursor gas during aCVD process. In one example, the substrate may be continuously exposedto the treatment gas during the CVD process. In another example, thesubstrate may be periodically exposed to the treatment gas during theCVD process. In another example, the substrate may be exposed to thetreatment gas prior to the CVD process.

In another embodiment, a method for depositing a material on a substratesurface is provided which includes exposing the substrate to a firstprecursor gas to deposit a material on the substrate at a firstdeposition rate during a vapor deposition process, wherein the firstprecursor gas contains a first precursor having the chemical formula ofML′_(x), where x is 1, 2, 3, 4, 5, 6, or greater, M is an elementselected from the group consisting of Ti, Zr, Hf, Nb, Ta, Mo, W, Ru, Co,Ni, Pd, Pt, Cu, Al, Ga, In, Si, Ge, Sn, P, As, and Sb, and each L′ isindependently a ligand selected from the group consisting of alkylamino,alkylimino, alkoxy, alkyl, alkene, alkyne, cyclopentadienyl,alkylcyclopentadienyl, pentadienyl, pyrrolyl, hydrogen, halogen,derivatives thereof, or combinations thereof, exposing the substrate toa treatment gas containing a hydrogenated ligand compound, wherein thehydrogenated ligand compound has the chemical formula of HL, where L isa ligand selected from the group consisting of alkylamino, alkylimino,alkoxy, alkyl, alkene, alkyne, cyclopentadienyl, alkylcyclopentadienyl,pentadienyl, pyrrolyl, or derivatives thereof, and depositing thematerial on the substrate at a second deposition rate during the vapordeposition process, wherein the second deposition rate is less than thefirst deposition rate. The vapor deposition process may further includeexposing the substrate sequentially to the first precursor gas and asecond precursor gas during the ALD process.

In many examples, the hydrogenated ligand compound within the treatmentgas has the chemical formula of HL, where L is a ligand such asalkylamino, alkylimino, alkoxy, alkyl, alkene, alkyne, cyclopentadienyl,alkylcyclopentadienyl, pentadienyl, pyrrolyl, or derivatives thereof.The first precursor gas may contain a first precursor having thechemical formula of ML′_(x), where x is 1, 2, 3, 4, 5, 6, or greater, Mis an element such as Ti, Zr, Hf, Nb, Ta, Mo, W, Ru, Co, Ni, Pd, Pt, Cu,Al, Ga, In, Si, Ge, Sn, P, As, or Sb, and each L′ is independently aligand such as alkylamino, alkylimino, alkoxy, alkyl, alkene, alkyne,cyclopentadienyl, alkylcyclopentadienyl, pentadienyl, pyrrolyl,hydrogen, halogen, derivatives thereof, or combinations thereof.

In some examples, the treatment gas contains a hydrogenated ligandcompound, such as an alkylamine compound having the chemical formula ofH₂NR or HNR′R″, where each R, R′, and R″ is independently methyl, ethyl,propyl, butyl, amyl, phenyl, aryl, isomers thereof, derivatives thereof,or combinations thereof. The alkylamine compound may be methylamine,dimethylamine, ethylamine, diethylamine, methylethylamine, propylamine,dipropylamine, butylamine, dibutylamine, isomers thereof, derivativesthereof, or combinations thereof. The treatment gas may further containat least one carrier gas such as ammonia, hydrogen, nitrogen, argon,helium, or combinations thereof. In one example the treatment gascontains dimethylamine, ammonia, and another carrier gas, such as argon.

In some embodiments, the alkylamino metal precursor gas contains analkylamino metal precursor having the chemical formula of ML′_(x), wherex is 1, 2, 3, 4, 5, 6, or greater, M may be a metal or other elementsuch as Ti, Zr, Hf, Ta, Mo, W, or Si, and each ligand L′ isindependently a ligand, such as an alkylamino ligand, which includeN(CH₃)₂, N(C₂H₅)₂, N(C₃H₇)₂, N(C₄H₉)₂, N(CH₃)(C₂H₅), isomers thereof,derivatives thereof, or combinations thereof. In some examples, themetal or element M may be Si, Ti, Zr, or Hf while x is usually 4. Inother examples, the alkylamino metal precursor is a tantalum precursorwith the metal M being Ta while x is usually 4 or 5. Examples oftantalum precursors include pentakis(dimethylamino) tantalum (PDMAT),pentakis(diethylamino) tantalum, pentakis(ethylmethylamino) tantalum,tert-butylimino tris(dimethylamino) tantalum, tert-butyliminotris(diethylamino) tantalum, tert-butylimino tris(ethylmethylamino)tantalum, tert-amylimino-tris(dimethylamino) tantalum,tert-amylimino-tris(diethylamino) tantalum,tert-amylimino-tris(ethylmethylamino) tantalum, or derivatives thereof.In one example, the tantalum precursor is PDMAT and the alkylaminecompound gas contains methylamine or dimethylamine.

In other examples, the hydrogenated ligand compound within the treatmentgas may be an alcohol compound having the chemical formula of ROH, whereR is methyl, ethyl, propyl, butyl, amyl, isomers thereof, or derivativesthereof. The alcohol compound may be methanol, ethanol, propanol,butanol, pentanol, isomers thereof, derivatives thereof, or combinationsthereof. In examples that the hydrogenated ligand compound is analcohol, the first precursor may contain an alkoxy ligand such as OCH₃,OC₂H₅, OC₃H₇, OC₄H₉, isomers thereof, or derivatives thereof. In otherexamples, the ligand L of the hydrogenated ligand compound may becyclopentadienyl, alkylcyclopentadienyl, pentadienyl, pyrrolyl, isomersthereof, or derivatives thereof and the ligand L′ of the first precursormay be cyclopentadienyl, alkylcyclopentadienyl, pentadienyl, pyrrolyl,isomers thereof, or derivatives thereof.

In one example, a method for depositing a material on a substratesurface is provided which includes exposing a substrate disposed withinthe processing chamber to a carrier gas having a continuous flow,introducing a treatment gas containing methylamine or dimethylamine tothe continuously flowing carrier gas to expose the substrate to thetreatment gas during a treatment process. The method further providesalternately or sequentially pulsing a tantalum precursor gas and anitrogen precursor gas into the continuously flowing carrier gas tosequentially expose the substrate to the tantalum and nitrogen precursorgases while depositing a tantalum nitride material on the substrateduring an ALD process. In one example, the tantalum precursor gascontains PDMAT and the nitrogen precursor gas contains ammonia.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the inventioncan be understood in detail, a more particular description of theinvention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of the invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 depicts a flow diagram of a method for depositing a tantalumnitride material in accordance with embodiments described herein.

DETAILED DESCRIPTION

Embodiments of the invention provide methods for depositing a materialon a substrate within a processing chamber during a vapor depositionprocess, such as an atomic layer deposition (ALD) process or a chemicalvapor deposition (CVD) process. Generally, the substrate may becontinuously or periodically exposed to a treatment gas containing areagent prior to and/or during the vapor deposition process. Thetreatment gas may be administered into the processing chamber and thesubstrate is exposed to the treatment gas prior to and/or during thevapor deposition process. The deposition rate of the material beingdeposited may be controlled by varying the amount of treatment gasexposed to the substrate. Therefore, the deposition rate may beadjusted, such as within a range from about 0.05 Å/cycle (Å per ALDcycle) to about 1.0 Å/cycle, for example, about 0.5 Å/cycle.

In one example, the method includes exposing the substrate to thetreatment gas to reduce the deposition rate of the material by about 95%or less during the ALD process. The material may be deposited on thesubstrate in the absence of the treatment gas at a first deposition rateduring the ALD process and in the presence of the treatment gas at asecond deposition rate during the ALD process. The second depositionrate may be about 95% or less of the first deposition rate. In otherexamples, the second deposition rate may be about 90% or less, about 80%or less, about 70% or less, or about 50% or less of the first depositionrate. In another example, the second deposition rate may be decreasedrelative to the first deposition rate by an amount within a range fromabout 0.05 Å/cycle to about 1.0 Å/cycle, such as about 0.5 Å/cycle.

In one embodiment, the substrate may be continuously or periodicallyexposed to a treatment gas containing a reagent, such as a hydrogenatedligand compound, during a treatment process and/or during the vapordeposition process. The hydrogenated ligand compound may be the sameligand as a free ligand formed from the metal-organic precursor usedduring the subsequent vapor deposition process. The free ligand isusually formed by hydrogenation or thermolysis during the depositionprocess. In one example, the substrate is exposed to an alkylaminecompound, such as dimethylamine (DMA) during a treatment process priorto and/or during a vapor deposition process utilizing a metal-organicchemical precursor, which may have alkylamino ligands, such aspentakis(dimethylamino) tantalum (PDMAT, ((CH₃)₂N)₅Ta).

In many examples, the treatment gas contains a hydrogenated ligandcompound having the chemical formula of HL, where L is a ligand such asalkylamino, alkylimino, alkoxy, alkyl, alkene, alkyne, cyclopentadienyl,alkylcyclopentadienyl, pentadienyl, pyrrolyl, or derivatives thereof.The chemical precursor gas contains a chemical precursor having thechemical formula of ML′_(x), where x is 1, 2, 3, 4, 5, 6, or greater, Mis an element such as Ti, Zr, Hf, Nb, Ta, Mo, W, Ru, Co, Ni, Pd, Pt, Cu,Al, Ga, In, Si, Ge, Sn, P, As, or Sb, and each L′ is independently aligand such as alkylamino, alkylimino, alkoxy, alkyl, alkene, alkyne,cyclopentadienyl, alkylcyclopentadienyl, pentadienyl, pyrrolyl,hydrogen, halogen, derivatives thereof, or combinations thereof.

In some embodiments, the method provides that the vapor depositionprocess is an ALD process and the substrate is sequentially exposed tothe alkylamino metal precursor gas and another chemical precursor gasduring the ALD process. In other embodiments, the vapor depositionprocess is a CVD process and the substrate is simultaneously exposed tothe alkylamino metal precursor gas and another chemical precursor gasduring the CVD process. In one example, the method provides exposing thesubstrate within the processing chamber to a treatment gas containing analkylamine compound prior to and/or during an ALD process, and exposingthe substrate sequentially to an alkylamino metal precursor gas and atleast one additional chemical precursor gas while depositing a materialon the substrate during the ALD process. In another example, the methodprovides continuously or periodically exposing the substrate to thetreatment gas containing the alkylamine compound while also exposing thesubstrate sequentially to an alkylamino metal precursor gas and anadditional chemical precursor gas while depositing the material on thesubstrate during the ALD process. The additional chemical precursor gasmay contain a nitrogen precursor, such as ammonia, which is used todeposit a metal nitride material, such as tantalum nitride.

In some examples, the treatment gas contains an alkylamine compoundhaving the chemical formula of H₂NR or HNR′R″, where each R, R′, and R″is independently methyl, ethyl, propyl, butyl, amyl, phenyl, aryl,isomers thereof, derivatives thereof, or combinations thereof. Thealkylamine compound may be methylamine, dimethylamine, ethylamine,diethylamine, methylethylamine, propylamine, dipropylamine, butylamine,dibutylamine, isomers thereof, derivatives thereof, or combinationsthereof. The treatment gas may further contain at least one carrier gassuch as ammonia, hydrogen, nitrogen, argon, helium, or combinationsthereof. In one example the treatment gas contains dimethylamine,ammonia, and another carrier gas, such as argon.

In some embodiments, the alkylamino metal precursor gas contains analkylamino metal precursor having the chemical formula of ML′_(x), wherex is 1, 2, 3, 4, 5, 6, or greater, M may be a metal or other elementsuch as Ti, Zr, Hf, Ta, Mo, W, or Si, and each ligand L′ isindependently a ligand, such as an alkylamino ligand, which includeN(CH₃)₂, N(C₂H₅)₂, N(C₃H₇)₂, N(C₄H₉)₂, N(CH₃)(C₂H₅), isomers thereof,derivatives thereof, or combinations thereof. In some examples, themetal or the element M may be Si, Ti, Zr, or Hf while x is usually 4. Inother examples, the alkylamino metal precursor is a tantalum precursorwith the metal M being Ta while x is usually 4 or 5. Examples oftantalum precursors include pentakis(dimethylamino) tantalum,pentakis(diethylamino) tantalum, pentakis(ethylmethylamino) tantalum,tert-butylimino tris(dimethylamino) tantalum, tert-butyliminotris(diethylamino) tantalum, tert-butylimino tris(ethylmethylamino)tantalum, tert-amylimino-tris(dimethylamino) tantalum,tert-amylimino-tris(diethylamino) tantalum,tert-amylimino-tris(ethylmethylamino) tantalum, or derivatives thereof.In one example, the tantalum precursor is PDMAT and the alkylaminecompound gas contains methylamine or dimethylamine.

In other examples, the hydrogenated ligand compound within the treatmentgas may be an alcohol compound having the chemical formula of ROH, whereR is methyl, ethyl, propyl, butyl, amyl, isomers thereof, or derivativesthereof. The alcohol compound may be methanol, ethanol, propanol,butanol, pentanol, isomers thereof, derivatives thereof, or combinationsthereof. In examples that the hydrogenated ligand compound is analcohol, the chemical precursor may contain an alkoxy ligand such asOCH₃, OC₂H₅, OC₃H₇, OC₄H₉, isomers thereof, or derivatives thereof. Inother examples, the ligand L of the hydrogenated ligand compound may becyclopentadienyl, alkylcyclopentadienyl, pentadienyl, pyrrolyl, isomersthereof, or derivatives thereof and the ligand L′ of the chemicalprecursor may be cyclopentadienyl, alkylcyclopentadienyl, pentadienyl,pyrrolyl, isomers thereof, or derivatives thereof.

In one example, a method for depositing a material on a substratesurface is provided which includes exposing a substrate disposed withinthe processing chamber to a carrier gas having a continuous flow,introducing a treatment gas containing methylamine or dimethylamine tothe continuously flowing carrier gas to expose the substrate to thetreatment gas during a treatment process. The method further providesalternately or sequentially pulsing a tantalum precursor gas and anitrogen precursor gas into the continuously flowing carrier gas tosequentially expose the substrate to the tantalum and nitrogen precursorgases while depositing a tantalum nitride material on the substrateduring an ALD process. In one example, the tantalum precursor gascontains PDMAT and the nitrogen precursor gas contains ammonia.

FIG. 1 depicts a flowchart of sequences for ALD process 100 fordepositing a material on a substrate in accordance with some embodimentsdescribed herein. ALD process 100 provides a continuous flow of acarrier gas administered into the processing chamber and exposed to asubstrate therein (step 104). The substrate may optionally be exposed toa treatment gas containing a reagent (step 106). ALD process 100includes sequentially exposing the substrate to the first precursor gas(step 108) and a second precursor gas (step 110). In one embodiment, thesubstrate may be exposed to the treatment gas, such as in step 106,prior to the ALD cycle of step 108 and 110. In another embodiment, thesubstrate may be continuously exposed to the treatment gas during theALD cycle. In another embodiment, the substrate may be periodicallyexposed to the treatment gas during the ALD cycle. In one example, atantalum nitride material may be deposited on the substrate.

At step 102, the processing chamber may be heated and pressurized to apredetermined temperature and pressure. The substrate and the substratepedestal may also be heated to predetermined temperatures. An exemplarytemperature of the processing chamber, the substrate, and/or thesubstrate pedestal during the treatment process and the depositionprocess may be within a range from about 100° C. to about 500° C.,preferably, from about 200° C. to about 400° C., and more preferably,from about 250° C. to about 300° C. The processing chamber may contain achamber body and a chamber lid, which each may independently be heatedto a temperature within a range from about 25° C. to about 300° C.,preferably, from about 30° C. to about 100° C., and more preferably,from about 40° C. to about 80° C. In one example, the processing chambermay have an internal pressure within a range from about 1 mTorr to about100 Torr, preferably, from about 1 Torr to about 50 Torr, and morepreferably, from about 5 Torr to about 20 Torr, such as about 10 Torr.

The substrate may be exposed to a continuous flow of a carrier gasadministered into the processing chamber at step 104 of ALD process 100.The carrier gas may have a gas flow rate within a range from about 0.5slm to about 20 slm, preferably, from about 1 slm to about 16 slm, andmore preferably, from about 2 slm to about 8 slm, such as about 4 slmduring step 104.

The substrate may be optionally exposed to a treatment gas during atreatment process at step 106 of ALD process 100. In one embodiment, thetreatment gas may be administered, delivered, or pulsed into theprocessing chamber and/or the continuous flow of a carrier gas withinthe processing chamber. The substrate may be continuously orperiodically/discontinuously exposed to the treatment gas. In oneexample, the treatment process provides exposing the substrate to atreatment gas containing a hydrogenated ligand compound, such as analkylamine compound. In one example, the alkylamine compound may bemethylamine, dimethylamine, or derivatives thereof.

The treatment gas containing the hydrogenated ligand compound may beexposed to the substrate with or without a carrier gas. In manyexamples, the treatment gas contains at least one carrier gas as well asthe hydrogenated ligand compound. The carrier gas of the treatment gasmay be ammonia, argon, nitrogen, hydrogen, helium, or mixtures thereof.In an alternative embodiment, such as for forming oxides or othermaterials, the carrier gas of the treatment gas may include oxygen,nitrous oxide, or air.

The substrate may be exposed to the treatment gas having a gas flow ratewithin a range from about 0.5 slm to about 20 slm, preferably, fromabout 1 slm to about 16 slm, and more preferably, from about 2 slm toabout 8 slm, such as about 4 slm during step 106. The treatment gas mayformed by flowing the carrier gas through an ampoule or a bubblercontaining the hydrogenated ligand compound. Alternatively, thetreatment gas may formed by co-flowing the hydrogenated ligand compoundwith the carrier gas. The hydrogenated ligand compound may have a gasflow rate within a range from about 5 sccm to about 1,000 sccm,preferably, from about 25 sccm to about 500 sccm, and more preferably,from about 50 sccm to about 150 sccm, such as about 100 sccm. In oneexample, the treatment gas contains an alkylamine compound, such asmethylamine, dimethylamine, or derivatives thereof, as well as at leastone carrier gas. In one example, the treatment gas may containdimethylamine with a flow rate of about 100 sccm and argon with a flowrate of about 4 slm. In another example, the treatment gas may containdimethylamine with a flow rate of about 20 sccm, ammonia with a flowrate of about 1 slm, and argon with a flow rate of about 8 slm. Theprocessing chamber and/or substrate may be exposed to the treatment gascontaining the hydrogenated ligand or other reagent for a time periodwithin a range from about 2 seconds to about 120 seconds, preferably,from about 5 seconds to about 60 seconds, for example, about 20 secondsor about 40 seconds.

In step 108, a pulse of a first chemical precursor is administered intothe processing chamber, pulsed into the stream of carrier gas, andadsorbed on the substrate surface. In one example, a tantalum precursoris pulsed into the stream of carrier gas and a monolayer of a tantalumprecursor is adsorbed on the substrate. Any remnants of the firstchemical precursor may be removed by the continuous flow of the purgegas and/or evacuation of an attached vacuum system.

The substrate is continuously exposed to the carrier gas and a pulse ofa second chemical precursor is added into the carrier gas during step110. In one example, the second chemical precursor is a nitrogenprecursor. The second chemical precursor reacts with the adsorbed layerof the first chemical precursor to form a deposited layer of material onthe substrate. In one example, the second chemical precursor is anitrogen precursor. The nitrogen precursor, such as ammonia, reacts withthe adsorbed layer of the first chemical precursor, such as the tantalumprecursor, to form a tantalum nitride layer on the substrate. Anyremnants of the second chemical precursor and any by-products (e.g.,organic compounds) may be removed by the continuous flow of the purgegas and/or evacuation of the attached vacuum system.

In embodiments described herein, the treatment gas may optionally beadministered, delivered, or pulsed into the stream of carrier gas, thetantalum precursor, and/or the nitrogen precursor while exposing thesubstrate prior to, during, or after steps 108 and/or 110.Alternatively, the treatment gas may optionally be administered,delivered, or pulsed independently into the processing chamber to exposethe substrate prior to, during, or after steps 108 and/or 110.Therefore, the substrate may be continuously or periodically exposed tothe treatment gas during any of the steps of ALD process 100. In oneexample, the substrate is exposed to the treatment gas containing ahydrogenated ligand compound, preferably, an alkylamine compound, suchas methylamine, dimethylamine, or derivatives thereof during any ofsteps 106, 108, and/or 110.

The deposition rate of the material being deposited may be controlled byvarying the amount of treatment gas exposed to the substrate during anyof steps 106, 108, and/or 110. Therefore, the deposition rate may beadjusted, such as within a range from about 0.05 Å/cycle (Å per ALDcycle) to about 1.0 Å/cycle. In one example, the deposition rate of thedeposited material is about 0.5 Å/cycle.

In other examples, the deposition rate of the deposited material on thesubstrate may be controlled or reduced by exposing the substrate to thetreatment gas prior to or during each ALD cycle of ALD process 100. Thedeposition rate of the deposited material may be reduced by about 95% orless, relative to depositing the material by the same ALD processwithout exposing the substrate to the treatment gas. In one embodiment,the material may be deposited on the substrate in the absence of thetreatment gas at a first deposition rate during an ALD process and inthe presence of the treatment gas at a second deposition rate during anyof steps 106, 108, and/or 110 of the ALD process 100. In one example,the second deposition rate may be about 95%, or less of the firstdeposition rate. In another example, the second deposition rate may beabout 90%, or less of the first deposition rate. In another example, thesecond deposition rate may be about 80%, or less of the first depositionrate. In another example, the second deposition rate may be about 70%,or less of the first deposition rate. In another example, the seconddeposition rate may be about 60%, or less of the first deposition rate.In another example, the second deposition rate may be about 50%, or lessof the first deposition rate. In another example, the second depositionrate may be within a range from about 0.05 Å/cycle to about 1.0 Å/cycle,such as about 0.5 Å/cycle.

At step 112, if the desired thickness of the deposited material has beenachieved, then the deposition process is ended at step 114. However,multiple ALD cycles of steps 106-112 are generally repeated beforeachieving the desired thickness of the deposited material. In oneexample, PDMAT and ammonia are sequentially pulsed for 40 cycles and thesubstrate is continuously exposed to DMA while depositing a tantalumnitride material with a thickness about 20 Å. In another example, PDMATand ammonia are sequentially pulsed for 40 cycles and the substrate isdiscontinuously exposed to DMA while depositing a tantalum nitridematerial with a thickness about 20 Å.

In an alternative embodiment, ALD process 100 may start with theadsorption of a monolayer of the second chemical precursor (e.g., anitrogen precursor) on the substrate followed by the absorption of amonolayer of the first chemical precursor (e.g., a tantalum precursor).In another embodiment, ALD process 100 may start with the adsorption ofa monolayer of the treatment gas and subsequently, sequential monolayersof the tantalum and nitrogen precursors on the substrate. Furthermore,in other examples, a pump evacuation alone between pulses of reactantgases and/or purge gases may be used to prevent mixing of the reactantgases.

In some examples, the PDMAT precursor may be heated within an ampoule, avaporizer, a bubbler, or a similar container prior to flowing into anALD processing chamber. The PDMAT may be heated to a temperature atleast 30° C., preferably within a range from about 45° C. to about 90°C., more preferably from about 50° C. to about 80° C., such as about 73°C. The preheated PDMAT precursor is retained in the carrier gas morethoroughly than if the PDMAT precursor was at room temperature (about20° C.). In order to heat the PDMAT precursor to a desired temperature,the ampoule, delivery lines, and valves on the ampoule and/or deliverylines may each be independently heated to a temperature within a rangefrom about 25° C. to about 300° C., preferably, from about 50° C. toabout 150° C., and more preferably, from about 70° C. to about 120° C.In one example, the sidewalls of the ampoule may be heated to about 85°C., the delivery lines may be heated to about 100° C., and the valvesmay be heated to about 95° C.

In some embodiments, during the treatment process and the depositionprocess, the processing chamber and the substrate may be maintainedapproximately below a thermal decomposition temperature of the selectedchemical precursor, such as the tantalum precursor PDMAT during aprocess to deposit a tantalum nitride material.

For clarity and ease of description, the method will be furtherdescribed as it relates to the deposition of a tantalum nitride barrierlayer using an ALD process. Pulses of a tantalum precursor or atantalum-containing compound, such as PDMAT may be introduced into theprocessing chamber. The tantalum precursor may be provided with the aidof a carrier gas or purge gas, which includes, but is not limited to,helium, argon, nitrogen, hydrogen, forming gas, or mixtures thereof.Pulses of a nitrogen precursor or a nitrogen-containing compound, suchas ammonia, are also introduced into the processing chamber. A carriergas may be used to deliver the nitrogen precursor. In one aspect, theflow of purge gas may be continuously provided by a gas sources (e.g.,tank or in-house) to act as a purge gas between the pulses of thetantalum precursor and of the nitrogen precursor and to act as a carriergas during the pulses of the tantalum precursor and the nitrogenprecursor. In other aspects, a pulse of purge gas may be provided aftereach pulse of the tantalum precursor and each pulse the nitrogenprecursor. Also, a constant purge or carrier gas may be flowing throughthe processing chamber during each of the deposition steps or halfreactions.

In one example, the substrate may be heated to a temperature within arange from about 250° C. to about 300° C. and the internal pressure ofthe chamber may be within a range from about 5 Torr to about 15 Torr.The substrate may be exposed to an argon carrier gas having a flow ratewithin a range from about 1,000 sccm to about 3,000 sccm, preferablyabout 1,500 sccm.

A tantalum precursor gas may be formed by flowing a carrier gas, such asargon, through the ampoule of preheated PDMAT a rate from about 200 sccmto about 2,000 sccm, for example, about 500 sccm. The PDMAT ismaintained at about 73° C. A tantalum precursor gas containing PDMAT andargon may be administered to the substrate surface for a period of timewithin a range from about 0.1 seconds to about 3.0 seconds, preferably,from about 0.5 seconds to about 1.5 seconds, for example, about 1second.

In some examples, the substrate is continuously exposed to a treatmentgas containing DMA while being exposed to the tantalum precursor gascontaining PDMAT. In other examples, the substrate is periodicallyexposed to a treatment gas containing DMA while being exposed to thetantalum precursor gas containing PDMAT. In other examples, thesubstrate is exposed to a treatment gas containing DMA prior to beingexposed to the tantalum precursor gas containing PDMAT. The treatmentgas containing DMA and the tantalum precursor gas containing PDMAT maybe independently flowed or co-flowed into the processing chamber and maybe independently exposed or simultaneously exposed to the substrate.

After the substrate is exposed to a pulse of PDMAT, the flow of carriergas may continue to purge for a period of time within a range from about0.2 seconds to about 5.0 seconds, preferably, from about 0.25 seconds toabout 1.5 seconds, for example, about 0.5 seconds. The attached vacuumsystem removes any remaining PDMAT during this purge step.

Subsequently, a pulse of a nitrogen precursor gas containing ammonia isadministered to the substrate surface. The nitrogen precursor gas mayinclude the nitrogen precursor in a carrier gas or may be solely thenitrogen precursor. In one example, the nitrogen precursor gas containsammonia and nitrogen. The nitrogen precursor gas containing ammonia maybe delivered a rate from about 1,000 sccm to about 3,000 sccm,preferably about 1,500 sccm and may be administered to the substratesurface for a period of time within a range from about 0.1 seconds toabout 3.0 seconds, preferably, from about 0.5 seconds to about 1.5seconds, for example about 1 second.

In some examples, the substrate is continuously exposed to the treatmentgas containing DMA while being exposed to the nitrogen precursor gascontaining ammonia. In other examples, the substrate is periodicallyexposed to the treatment gas containing DMA while being exposed to thenitrogen precursor gas containing ammonia. In other examples, thesubstrate is exposed to the treatment gas containing DMA prior to beingexposed to the nitrogen precursor gas containing ammonia. The treatmentgas containing DMA and the nitrogen precursor gas containing ammonia maybe independently flowed or co-flowed into the processing chamber and maybe independently exposed or simultaneously exposed to the substrate.

After the pulse of the nitrogen precursor gas containing ammonia, theflow of the carrier gas may continue for a period of time within a rangefrom about 0.2 seconds to about 5.0 seconds, preferably, from about 0.25seconds to about 1.5 seconds, for example, about 0.5 seconds. The vacuumsystem removes any remaining nitrogen precursor and/or any by-productsformed during the reaction.

The ALD cycle may be repeated until a predetermined thickness of thedeposited material, such as tantalum nitride, is achieved, such aswithin a range from about 5 Å to about 200 Å, preferably, from about 10Å to about 30 Å, such as about 20 Å for a barrier layer.

The time duration for each pulse of tantalum precursor gas, pulse of thenitrogen precursor gas, and pulse of purge gas between pulses of thereactants are variable and depend on the volume capacity of a depositionchamber employed as well as a vacuum system coupled thereto. Forexample, (1) a lower chamber pressure of a gas will require a longerpulse time, (2) a lower gas flow rate will require a longer time forchamber pressure to rise and stabilize requiring a longer pulse time,and (3) a large-volume chamber will take longer to fill, longer forchamber pressure to stabilize thus requiring a longer pulse time.Similarly, time between each pulse is also variable and depends onvolume capacity of the processing chamber as well as the vacuum systemcoupled thereto. In general, the time duration of a pulse of thetantalum precursor gas or the nitrogen precursor gas should be longenough for adsorption or reaction of a monolayer of the compound. In oneaspect, a pulse of a tantalum precursor gas may still be in theprocessing chamber when a pulse of a nitrogen precursor gas enters. Thetreatment gas may still be in the processing chamber along with thepulse of the tantalum precursor gas and/or the pulse of the nitrogenprecursor gas. In general, the duration of the purge gas and/or pumpevacuation should be long enough to prevent the pulses of the tantalumprecursor gas and the nitrogen precursor gas from mixing together in thereaction zone.

In another embodiment, the substrate may be exposed to the treatment gasprior to or during the deposition of other materials on a substrate. Inone example, the hydrogenated ligand compound may be an alkylaminecompound, such as methylamine or dimethylamine, while PDMAT may be usedas a tantalum precursor to form other tantalum-containing material, suchas tantalum oxide, tantalum silicon nitride, tantalum boron nitride,tantalum phosphorous nitride, tantalum oxynitride, or tantalum silicate.A more detailed description of a process to form ternary or quaternaryelemental tantalum-containing materials is described in commonlyassigned U.S. Pat. No. 7,081,271, which is herein incorporated byreference in its entirety.

Process 100 may be modified in order to obtain other tantalum-containingmaterials. For example, the substrate may be exposed to the treatmentgas prior to or during the deposition of a tantalum silicon nitridematerial, which may be formed if the substrate is exposed to a pulse ofa silicon precursor as an additional step of the ALD cycle containingthe pulses of the tantalum precursor gas and a nitrogen precursor.Similar, the substrate may be exposed to the treatment gas prior to orduring the deposition of a tantalum oxynitride material, which may beformed if the substrate is exposed to a pulse of an oxygen precursor asan additional step of the ALD cycle containing the pulses of thetantalum precursor gas and a nitrogen precursor. In another example, thesubstrate may be exposed to the treatment gas prior to or during thedeposition of a tantalum silicate material, which may be formed if thesubstrate is exposed to a pulse of the tantalum precursor gas, a pulseof a silicon precursor, and a pulse of an oxygen precursor during theALD cycle. In another example, the substrate may be exposed to thetreatment gas prior to or during the deposition of a tantalum oxidematerial, which may be formed if the substrate is exposed to a pulse ofthe tantalum precursor gas and a pulse of an oxygen precursor during theALD cycle. In another example, the substrate may be exposed to thetreatment gas prior to or during the deposition of a tantalumphosphorous nitride material, which may be formed if the substrate isexposed to a pulse of the tantalum precursor gas, a pulse of a nitrogenprecursor and a pulse of a phosphorous precursor (e.g., phosphine)during the ALD cycle. In another example, the substrate may be exposedto the treatment gas prior to or during the deposition of a tantalumboron nitride material, which may be formed if the substrate is exposedto a pulse of the tantalum precursor gas, a pulse of a nitrogenprecursor and a pulse of a boron precursor (e.g., diborane) during theALD cycle.

In one embodiment, the substrate may be exposed to the treatment gasprior to or during the deposition of a tantalum nitride material, whichmay be formed or deposited with the chemical formula of TaN_(x), where xis within a range from about 0.4 to about 2.0. In some examples, thetantalum nitride materials may be formed with empirical formulas of TaN,Ta₃N₅, Ta₂N, or Ta₆N_(2.57). The tantalum nitride materials may bedeposited as amorphous or crystalline materials. The ALD processprovides stoichiometric control during the deposition of the tantalumnitride materials. The stoichiometry may be altered by variousprocedures following the deposition process, such as when Ta₃N₅ isthermally annealed to form TaN. The ratio of the precursors may bealtered during deposition to control the stoichiometry of the tantalumnitride materials.

In the examples above, the various tantalum materials, such as tantalumnitride, may be formed by ALD processes which utilize the tantalumprecursor PDMAT, the nitrogen precursor ammonia, and a treatment gascontaining a hydrogenated ligand compound, such as dimethylamine.However, other chemical precursors and hydrogenated ligand compounds arewithin the scope of embodiments of the invention.

An important characteristic for a chemical precursor used in a vapordeposition process is to have a favorable vapor pressure. The chemicalprecursor may have a gaseous state, a liquid state, or a solid state atambient temperature and/or pressure. However, within the vapordeposition system, precursors are volatilized to a gas and delivered tothe ALD or CVD processing chamber. The chemical precursors are usuallyheated prior to being delivered into the processing chamber.

Tantalum precursors may contain ligands such as alkylamino, alkylimino,cyclopentadienyl, alkylcyclopentadienyl, pentadienyl, alkyl, alkene,alkyne, alkoxyl, isomers thereof, derivatives thereof, or combinationsthereof. Alkylamino tantalum compounds used as tantalum precursorsinclude (RR′N)₅Ta, where each of R or R′ is independently hydrogen,methyl, ethyl, propyl, or butyl. Alkylimino tantalum compounds used astantalum precursors include (RN)(R′R″N)₃Ta, where each of R, R′, or R″is independently hydrogen, methyl, ethyl, propyl, butyl, or pentyl(amyl).

Exemplary tantalum precursors include pentakis(dimethylamino) tantalum(PDMAT, (Me₂N)₅Ta), pentakis(diethylamino) tantalum (PDEAT, (Et₂N)₅Ta),pentakis(ethylmethylamino) tantalum (PEMAT, (EtMeN)₅Ta), tert-butyliminotris(dimethylamino) tantalum (TBTDMT, (^(t)BuN)Ta(NMe₂)₃),tert-butylimino tris(diethylamino) tantalum (TBTDET,(^(t)BuN)Ta(NEt₂)₃), tert-butylimino tris(ethylmethylamino) tantalum(TBTEMT, (^(t)BuN)Ta(NMeEt)₃), tert-amylimino-tris(dimethylamino)tantalum (TAIMATA, (^(t)AmyIN)Ta(NMe₂)₃),tert-amylimino-tris(diethylamino) tantalum ((^(t)AmyIN)Ta(NEt₂)₃),tert-amylimino-tris(ethylmethylamino) tantalum ((^(t)AmyIN)Ta(NEtMe)₃),bis(cyclopentadienyl) tantalum trihydride (Cp₂TaH₃),bis(methylcyclopentadienyl) tantalum trihydride ((MeCp)₂TaH₃),bis(pentamethylcyclopentadienyl) tantalum trihydride ((Me₅Cp)₂TaH₃),tantalum methoxide ((MeO)₅Ta), tantalum ethoxide ((EtO)₅Ta), tantalumpropoxide ((PrO)₅Ta), tantalum butoxide ((BuO)₅Ta), isomers thereof, orderivatives thereof.

“TAIMATA” is used herein to describetertiaryamylimino-tris(dimethylamino) tantalum with the chemical formula(^(t)AmyIN)Ta(NMe₂)₃, wherein ^(t)Amyl is the tertiaryamyl (tert-amyl)group (C₅H₁₁— or CH₃CH₂C(CH₃)₂—). In one embodiment, a tantalumprecursor gas may be formed by heating a liquid TAIMATA precursor in avaporizer, a bubbler or an ampoule to a temperature of at least 30° C.,preferably to a temperature within a range from about 50° C. to about80° C. A carrier gas may be flown across or bubbled through the heatedTAIMATA to form a tantalum precursor gas.

Besides tantalum precursors, other chemical precursors may also be usedin vapor deposition processes, as described by embodiments herein.Exemplary chemical precursors that may also be used in vapor deposition(e.g., ALD or CVD) processes include titanium precursors, tungstenprecursors, hafnium precursors, zirconium precursors, aluminumprecursors, cobalt precursors, ruthenium precursors, copper precursors,silicon precursors, nitrogen precursors, oxygen precursors, as well asother chemical precursors. Materials that may be formed or depositedinclude a variety of metals, nitrides, oxides, silicides, includingmetallic tantalum, tantalum nitride, tantalum oxide, tantalumoxynitride, tantalum silicide, tantalum silicide nitride, metallictitanium, titanium nitride, titanium oxide, titanium oxynitride,titanium silicide, titanium silicide nitride, metallic tungsten,tungsten nitride, tungsten oxide, tungsten boronitride, tungstensilicide, tungsten silicide nitride, tungsten boride, metallic hafnium,hafnium nitride, hafnium oxide, hafnium oxynitride, hafnium silicide,hafnium silicon nitride, hafnium silicate, hafnium silicon oxynitride,metallic zirconium, zirconium nitride, zirconium oxide, zirconiumoxynitride, zirconium silicide, zirconium silicon nitride, zirconiumsilicate, zirconium silicon oxynitride, metallic aluminum, aluminumnitride, aluminum oxide, aluminum oxynitride, aluminum silicide,aluminum silicon nitride, aluminum silicate, aluminum siliconoxynitride, metallic cobalt, cobalt silicide, metallic ruthenium,metallic copper, copper alloys, derivatives thereof, alloys thereof, orcombinations thereof.

In another embodiment, the treatment gas contains a hydrogenated ligandcompound having the chemical formula of HL, where L is a ligand such asalkylamino, alkylimino, alkoxy, alkyl, alkene, alkyne, cyclopentadienyl,alkylcyclopentadienyl, pentadienyl, pyrrolyl, or derivatives thereof. Insome examples, such as when the metal precursor is an alkylamino metalprecursor, the treatment gas contains a hydrogenated ligand compoundwhich may be an alkylamine compound having the chemical formula of H₂NRor HNR′R″, where each R, R′, and R″ is independently methyl, ethyl,propyl, butyl, amyl, phenyl, aryl, isomers thereof, derivatives thereof,or combinations thereof. The alkylamine compound may be methylamine,dimethylamine, ethylamine, diethylamine, methylethylamine, propylamine,dipropylamine, butylamine, dibutylamine, isomers thereof, derivativesthereof, or combinations thereof. In some examples, the treatment gasfurther contains at least one carrier gas such as ammonia, hydrogen,nitrogen, argon, helium, or combinations thereof. In one example, thetreatment gas contains dimethylamine, ammonia, and another carrier gas,such as argon.

In other examples, the treatment gas contains a hydrogenated ligandcompound which may be an alcohol compound having the chemical formula ofROH, where R is methyl, ethyl, propyl, butyl, amyl, isomers thereof, orderivatives thereof. The alcohol compound may be methanol, ethanol,propanol, butanol, pentanol, isomers thereof, derivatives thereof, orcombinations thereof. In other examples, the chemical precursor containsan alkoxy ligand such as OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, isomers thereof, orderivatives thereof.

In other embodiments, the precursor gas contains a chemical precursorhaving the chemical formula of ML′_(x), where x is 1, 2, 3, 4, 5, 6, orgreater, M is an element such as Ti, Zr, Hf, Nb, Ta, Mo, W, Ru, Co, Ni,Pd, Pt, Cu, Al, Ga, In, Si, Ge, Sn, P, As, or Sb, and each L′ isindependently a ligand such as alkylamino, alkylimino, alkoxy, alkyl,alkene, alkyne, cyclopentadienyl, alkylcyclopentadienyl, pentadienyl,pyrrolyl, hydrogen, halogen, derivatives thereof, or combinationsthereof.

In one embodiment, the ligand L of the hydrogenated ligand compound maybe cyclopentadienyl, alkylcyclopentadienyl, pentadienyl, pyrrolyl,isomers thereof, or derivatives thereof and the ligand L′ of thechemical precursor may be cyclopentadienyl, alkylcyclopentadienyl,pentadienyl, pyrrolyl, isomers thereof, or derivatives thereof.

In some examples, the precursor gas contains the alkylamino metalprecursor gas contains an alkylamino metal precursor having the chemicalformula of ML′_(x), where x is 1, 2, 3, 4, 5, 6, or greater, M may be ametal or other element such as Ti, Zr, Hf, Ta, Mo, W, or Si, and eachligand L′ is independently a ligand, such as an alkylamino ligand, whichinclude N(CH₃)₂, N(C₂H₅)₂, N(C₃H₇)₂, N(C₄H₉)₂, N(CH₃)(C₂H₅), isomersthereof, derivatives thereof, or combinations thereof. In some examples,metal/element M may be Si, Ti, Zr, or Hf while x is usually 4. In otherexamples, the alkylamino metal precursor is a tantalum precursor withmetal M being Ta while x is usually 4 or 5.

In other examples, the hydrogenated ligand compound may be an alcoholcompound having the chemical formula of ROH, where R is methyl, ethyl,propyl, butyl, amyl, isomers thereof, or derivatives thereof. Thealcohol compound may be methanol, ethanol, propanol, butanol, pentanol,isomers thereof, derivatives thereof, or combinations thereof. In otherexamples, the first precursor contains an alkoxy ligand such as OCH₃,OC₂H₅, OC₃H₇, OC₄H₉, isomers thereof, or derivatives thereof. In otherexamples, the ligand L of the hydrogenated ligand compound may becyclopentadienyl, alkylcyclopentadienyl, pentadienyl, pyrrolyl, isomersthereof, or derivatives thereof and the ligand L′ of the first precursormay be cyclopentadienyl, alkylcyclopentadienyl, pentadienyl, pyrrolyl,isomers thereof, or derivatives thereof.

Titanium precursors useful for depositing materials as described hereininclude tetrakis(dimethylamino) titanium (TDMAT),tetrakis(ethylmethylamino) titanium (TEMAT), tetrakis(diethylamino)titanium (TDEAT), or derivatives thereof.

Tungsten precursors useful for depositing materials as described hereininclude bis(tert-butylimino)-bis(dimethylamino) tungsten ((^(t)BuN)₂W(NMe₂)₂), bis(tert-butylimino)-bis(diethylamino) tungsten((^(t)BuN)₂W(NEt₂)₂), bis(tert-butylimino)-bis(ethylmethylamino)tungsten ((^(t)BuN)₂W(NEtMe)₂), or derivatives thereof.

Hafnium alkylamino compounds useful as hafnium precursors include(RR′N)₄Hf, where each R and R′ is independently hydrogen, methyl, ethyl,propyl, butyl, amyl, or isomers thereof. Hafnium precursors useful fordepositing materials as described herein include tetrakis(diethylamino)hafnium ((Et₂N)₄Hf, TDEAH), tetrakis(dimethylamino) hafnium ((Me₂N)₄Hf,TDMAH), tetrakis(ethylmethylamino) hafnium ((EtMeN)₄Hf, TEMAH), hafniumtetramethoxide ((MeO)₄Hf), hafnium tetraethoxide ((EtO)₄Hf), hafniumtetrapropoxide ((PrO)₄Hf), hafnium tetrabutoxide ((BuO)₄Hf), isomersthereof, or derivatives thereof. Other hafnium precursors may includehafnium chloride (HfCI₄), hafnium iodide (Hfl₄), (^(t)BuC₅H₄)₂HfCl₂,(C₅H₅)₂HfCl₂, (EtC₅H₄)₂HfCl₂, (Me₅C₅)₂HfCl₂, (Me₅C₅)HfCl₃,(^(i)PrC₅H₄)₂HfCl₂, (^(i)PrC₅H₄)HfCl₃, (^(t)BuC₅H₄)₂HfMe₂, (acac)₄Hf,(hfac)₄Hf, (tfac)₄Hf, (thd)₄Hf, (NO₃)₄Hf, or derivatives thereof.

Zirconium alkylamino compounds useful as zirconium precursors include(RR′N)₄Zr, where each R and R′ is independently hydrogen, methyl, ethyl,propyl, butyl, amyl, or isomers thereof. Zirconium precursors useful fordepositing materials as described herein include tetrakis(diethylamino)zirconium ((Et₂N)₄Zr), tetrakis(dimethylamino) zirconium ((Me₂N )₄Zr),tetrakis(ethylmethylamino) zirconium ((EtMeN)₄Zr), zirconiumtetramethoxide ((MeO)₄Zr), zirconium tetraethoxide ((EtO)₄Zr), zirconiumtetrapropoxide ((PrO)₄Zr), zirconium tetrabutoxide ((BuO)₄Zr), isomersthereof, or derivatives thereof. Other zirconium precursors may includezirconium chloride (ZrCl₄), zirconium iodide (Zrl₄), (^(t)BuC₅H₄)₂ZrCl₂,(C₅H₅)₂ZrCl₂, (EtC₅H₄)₂ZrCl₂, (Me₅C₅)₂ZrCl₂, (Me₅C₅)ZrCl₃,(^(i)PrC₅H₄)₂ZrCl₂, (^(i)PrC₅H₄)ZrCl₃(^(t)BuC₅H₄)₂ZrMe₂, (acac)₄Zr,(Zrac)₄Zr, (tfac)₄Zr, (thd)₄Zr, (NO₃)₄Zr, or derivatives thereof.

Aluminum precursors useful for depositing materials as described hereininclude aluminum methoxide ((MeO)₃Al), aluminum ethoxide ((EtO)₃Al),aluminum propoxide ((PrO)₃Al), aluminum butoxide ((BuO)₃Al), orderivatives thereof.

Silicon precursors useful for depositing materials as described hereininclude silane compounds, alkylamino silane compounds, silanol, oralkoxysilane compounds, as well as other silicon containing compounds.Alkylamino silane compounds useful as silicon precursors include(RR′N)_(4-n)SiH_(n), where R or R′ are independently hydrogen, methyl,ethyl, propyl, butyl, amyl, isomers thereof, or derivatives thereof andn is 0, 1, 2, or 3. Alkoxy silane compounds may be described by thegeneric chemical formula (RO)_(4-n)SiL_(n), where R is methyl, ethyl,propyl, butyl, amyl, isomers thereof, or derivatives thereof and L is H,OH, F, Cl, Br, I, methyl, ethyl, propyl, butyl, or mixtures thereof, andn is 0, 1, 2, or 3. Silicon precursors may includetetrakis(dimethylamino) silane ((Me₂N)₄Si, DMAS), tris(dimethylamino)silane ((Me₂N)₃SiH, Tris-DMAS), bis(dimethylamino) silane ((Me₂N)₂SiH₂),dimethylamino silane ((Me₂N)SiH₃), tetrakis(diethylamino) silane((Et₂N)₄Si)), tris(diethylamino) silane ((Et₂N)₃SiH),tetrakis(methylethylamino) silane ((MeEtN)₄Si), tris(methylethylamino)silane ((MeEtN)₃SiH), tetramethoxysilane ((MeO)₄Si), tetraethoxysilane((EtO)₄Si), isomers thereof, derivatives thereof, or combinationsthereof. Other silicon precursors that may be used in vapor depositionprocesses described herein include silane (SiH₄), disilane (Si₂H₆),tetrachlorosilane (SiCl₄), hexachlorodisilane (Si₂Cl₆), tetraisocyanatesilane (Si(NCO)₄), trisocyanate methylsilane (MeSi(NCO)₃), orderivatives thereof.

In another embodiment, a family of ruthenium precursors useful to form aruthenium material during the deposition process described hereinincludes pyrrolyl ruthenium precursors. During a treatment process ofthe processing chamber and/or the substrate, the hydrogenated ligandcompound within the treatment gas may be a hydrogenated pyrrolyl ligand,pyridine, or derivatives thereof. In one example, a pyrrolyl rutheniumprecursor contains ruthenium and at least one pyrrolyl ligand or atleast one pyrrolyl derivative ligand. A pyrrolyl ruthenium precursor mayhave a pyrrolyl ligand, such as, for example:

where R₁, R₂, R₃, R₄, and R₅ is each independently absent, hydrogen, analkyl group (e.g., methyl, ethyl, propyl, butyl, amyl, or higher), anamine group, an alkoxy group, an alcohol group, an aryl group, anotherpyrrolyl group (e.g., 2,2′-bipyrrolyl), a pyrazole group, derivativesthereof, or combinations thereof. The pyrrolyl ligand may have any twoor more of R₁, R₂, R₃, R₄, and R₅ connected together by a chemicalgroup. For example, R₂ and R₃ may be a portion of a ring structure suchas an indolyl group or derivative thereof. A pyrrolyl rutheniumprecursor as used herein refers to any chemical compound containingruthenium and at least one pyrrolyl ligand or at least one derivative ofa pyrrolyl ligand. In some examples, a pyrrolyl ruthenium precursor mayinclude bis(tetramethylpyrrolyl) ruthenium, bis(2,5-dimethylpyrrolyl)ruthenium, bis(2,5-diethylpyrrolyl) ruthenium, bis(tetraethylpyrrolyl)ruthenium, pentadienyl tetramethylpyrrolyl ruthenium, pentadienyl2,5-dimethylpyrrolyl ruthenium, pentadienyl tetraethylpyrrolylruthenium, pentadienyl 2,5-diethylpyrrolyl ruthenium,1,3-dimethylpentadienyl pyrrolyl ruthenium, 1,3-diethylpentadienylpyrrolyl ruthenium, methylcyclopentadienyl pyrrolyl ruthenium,ethylcyclopentadienyl pyrrolyl ruthenium, 2-methylpyrrolyl pyrrolylruthenium, 2-ethylpyrrolyl pyrrolyl ruthenium, or derivatives thereof.

A pyrrolyl ligand, as used herein, may be abbreviated by “py” and apyrrolyl derivative ligand may be abbreviated by “R-py.” Exemplarypyrrolyl ruthenium precursors useful to form a ruthenium material duringthe deposition process described herein include alkyl pyrrolyl rutheniumprecursors (e.g., (Re-py)Ru), bis(pyrrolyl) ruthenium precursors (e.g.,(py)₂Ru) and dienyl pyrrolyl ruthenium precursors (e.g., (Cp)(py)Ru).Examples of alkyl pyrrolyl ruthenium precursors include methylpyrrolylruthenium, ethylpyrrolyl ruthenium, propylpyrrolyl ruthenium,dimethylpyrrolyl ruthenium, diethylpyrrolyl ruthenium, dipropylpyrrolylruthenium, trimethylpyrrolyl ruthenium, triethylpyrrolyl ruthenium,tetramethylpyrrolyl ruthenium, tetraethylpyrrolyl ruthenium, orderivatives thereof. Examples of bis(pyrrolyl) ruthenium precursorsinclude bis(pyrrolyl) ruthenium, bis(methylpyrrolyl) ruthenium,bis(ethylpyrrolyl) ruthenium, bis(propylpyrrolyl) ruthenium,bis(dimethylpyrrolyl) ruthenium, bis(diethylpyrrolyl) ruthenium,bis(dipropylpyrrolyl) ruthenium, bis(trimethylpyrrolyl) ruthenium,bis(triethylpyrrolyl) ruthenium, bis(tetramethylpyrrolyl) ruthenium,bis(tetraethylpyrrolyl) ruthenium, methylpyrrolyl pyrrolyl ruthenium,ethylpyrrolyl pyrrolyl ruthenium, propylpyrrolyl pyrrolyl ruthenium,dimethylpyrrolyl pyrrolyl ruthenium, diethylpyrrolyl pyrrolyl ruthenium,dipropylpyrrolyl pyrrolyl ruthenium, trimethylpyrrolyl pyrrolylruthenium, triethylpyrrolyl pyrrolyl ruthenium, tetramethylpyrrolylpyrrolyl ruthenium, tetraethylpyrrolyl pyrrolyl ruthenium, orderivatives thereof.

A dienyl pyrrolyl ruthenium precursor contains at least one dienylligand and at least one pyrrolyl ligand. The dienyl ligand may contain acarbon backbone with as little as four carbon atoms or as many as aboutten carbon atoms, preferably, about five or six. The dienyl ligand mayhave a ring structure (e.g., cyclopentadienyl) or may be an open alkylchain (e.g., pentadienyl). Also, dienyl ligand may contain no alkylgroups, one alkyl group, or many alkyl groups.

In one embodiment, the dienyl pyrrolyl ruthenium precursor contains apentadienyl ligand or an alkylpentadienyl ligand. Examples ofpentadienyl pyrrolyl ruthenium precursors include pentadienyl pyrrolylruthenium, pentadienyl methylpyrrolyl ruthenium, pentadienylethylpyrrolyl ruthenium, pentadienyl propylpyrrolyl ruthenium,pentadienyl dimethylpyrrolyl ruthenium, pentadienyl diethylpyrrolylruthenium, pentadienyl dipropylpyrrolyl ruthenium, pentadienyltrimethylpyrrolyl ruthenium, pentadienyl triethylpyrrolyl ruthenium,pentadienyl tetramethylpyrrolyl ruthenium, pentadienyltetraethylpyrrolyl ruthenium, or derivatives thereof. Examples ofalkylpentadienyl pyrrolyl ruthenium precursors include alkylpentadienylpyrrolyl ruthenium, alkylpentadienyl methylpyrrolyl ruthenium,alkylpentadienyl ethylpyrrolyl ruthenium, alkylpentadienylpropylpyrrolyl ruthenium, alkylpentadienyl dimethylpyrrolyl ruthenium,alkylpentadienyl diethylpyrrolyl ruthenium, alkylpentadienyldipropylpyrrolyl ruthenium, alkylpentadienyl trimethylpyrrolylruthenium, alkylpentadienyl triethylpyrrolyl ruthenium, alkylpentadienyltetramethylpyrrolyl ruthenium, alkylpentadienyl tetraethylpyrrolylruthenium, or derivatives thereof.

In another embodiment, the dienyl pyrrolyl ruthenium precursor containsa cyclopentadienyl ligand or an alkylcyclopentadienyl ligand. Examplesof cyclopentadienyl pyrrolyl ruthenium precursors includecyclopentadienyl pyrrolyl ruthenium, cyclopentadienyl methylpyrrolylruthenium, cyclopentadienyl ethylpyrrolyl ruthenium, cyclopentadienylpropylpyrrolyl ruthenium, cyclopentadienyl dimethylpyrrolyl ruthenium,cyclopentadienyl diethylpyrrolyl ruthenium, cyclopentadienyldipropylpyrrolyl ruthenium, cyclopentadienyl trimethylpyrrolylruthenium, cyclopentadienyl triethylpyrrolyl ruthenium, cyclopentadienyltetramethylpyrrolyl ruthenium, cyclopentadienyl tetraethylpyrrolylruthenium, or derivatives thereof. Examples of alkylcyclopentadienylpyrrolyl ruthenium precursors include alkylcyclopentadienyl pyrrolylruthenium, alkylcyclopentadienyl methylpyrrolyl ruthenium,alkylcyclopentadienyl ethylpyrrolyl ruthenium, alkylcyclopentadienylpropylpyrrolyl ruthenium, alkylcyclopentadienyl dimethylpyrrolylruthenium, alkylcyclopentadienyl diethylpyrrolyl ruthenium,alkylcyclopentadienyl dipropylpyrrolyl ruthenium, alkylcyclopentadienyltrimethylpyrrolyl ruthenium, alkylcyclopentadienyl triethylpyrrolylruthenium, alkylcyclopentadienyl tetramethylpyrrolyl ruthenium,alkylcyclopentadienyl tetraethylpyrrolyl ruthenium, or derivativesthereof.

In another embodiment, a ruthenium precursor may contain no pyrrolylligand or pyrrolyl derivative ligand, but instead, contains at least oneopen chain dienyl ligand, such as CH₂CRCHCRCH₂, where R is independentlyan alkyl group or hydrogen. A ruthenium precursor may have twoopen-chain dienyl ligands, such as pentadienyl or heptadienyl. Abis(pentadienyl) ruthenium compound has a generic chemical formula(CH₂CRCHCRCH₂)₂Ru, where R is independently an alkyl group or hydrogen.Usually, R is independently hydrogen, methyl, ethyl, propyl or butyl.Therefore, ruthenium precursors may include bis(dialkylpentadienyl)ruthenium compounds, bis(alkylpentadienyl) ruthenium compounds,bis(pentadienyl) ruthenium compounds, or combinations thereof. Examplesof ruthenium precursors include bis(2,4-dimethylpentadienyl) ruthenium,bis(2,4-diethylpentadienyl) ruthenium, bis(2,4-diisopropylpentadienyl)ruthenium, bis(2,4-ditertbutylpentadienyl) ruthenium,bis(methylpentadienyl)ruthenium, bis(ethylpentadienyl) ruthenium,bis(isopropylpentadienyl) ruthenium, bis(tertbutylpentadienyl)ruthenium, derivatives thereof, or combinations thereof. In someembodiments, other ruthenium precursors includetris(2,2,6,6-tetramethyl-3,5-heptanedionato) ruthenium, dicarbonylpentadienyl ruthenium, ruthenium acetyl acetonate,2,4-dimethylpentadienyl cyclopentadienyl ruthenium,bis(2,2,6,6-tetramethyl-3,5-heptanedionato) (1,5-cyclooctadiene)ruthenium, 2,4-dimethylpentadienyl methylcyclopentadienyl ruthenium,1,5-cyclooctadiene cyclopentadienyl ruthenium, 1,5-cyclooctadienemethylcyclopentadienyl ruthenium, 1,5-cyclooctadieneethylcyclopentadienyl ruthenium, 2,4-dimethylpentadienylethylcyclopentadienyl ruthenium, 2,4-dimethylpentadienylisopropylcyclopentadienyl ruthenium, bis(N,N-dimethyl 1,3-tetramethyldiiminato) 1,5-cyclooctadiene ruthenium, bis(N,N-dimethyl 1,3-dimethyldiiminato) 1,5-cyclooctadiene ruthenium, bis(allyl) 1,5-cyclooctadieneruthenium, η⁶-C₆H₆ 1,3-cyclohexadiene ruthenium,bis(1,1-dimethyl-2-aminoethoxylato) 1,5-cyclooctadiene ruthenium,bis(1,1-dimethyl-2-aminoethylaminato) 1,5-cyclooctadiene ruthenium,bis(cyclopentadienyl) ruthenium, bis(methylcyclopentadienyl) ruthenium,bis(ethylcyclopentadienyl) ruthenium, andbis(pentamethylcyclopentadienyl) ruthenium, or derivatives thereof.

Cobalt precursors useful for depositing materials as described hereininclude cobalt carbonyl complexes, cobalt amidinates compounds,cobaltocene compounds, cobalt dienyl complexes, cobalt nitrosylcomplexes, derivatives thereof, complexes thereof, plasma thereof, orcombinations thereof. In some embodiments, cobalt materials may bedeposited by CVD and ALD processes further described in commonlyassigned U.S. Pat. Nos. 7,1164,846 and 7,404,985, which are hereinincorporated by reference.

In some embodiments, cobalt carbonyl compounds or complexes may beutilized as cobalt precursors. Cobalt carbonyl compounds or complexeshave the general chemical formula (CO)_(x)Co_(y)L_(z), where X may be 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, Y may be 1, 2, 3, 4, or 5, and Zmay be 1, 2, 3, 4, 5, 6, 7, or 8. The group L is absent, one ligand ormultiple ligands, that may be the same ligand or different ligands, andinclude cyclopentadienyl, alkylcyclopentadienyl (e.g.,methylcyclopentadienyl or pentamethylcyclopentadienyl), pentadienyl,alkylpentadienyl, cyclobutadienyl, butadienyl, ethylene, allyl (orpropylene), alkenes, dialkenes, alkynes, acetylene, butylacetylene,nitrosyl, ammonia, or derivatives thereof.

In one embodiment, dicobalt hexacarbonyl acetyl compounds may be used toform cobalt materials (e.g., cobalt layer 220) during a depositionprocess. Dicobalt hexacarbonyl acetyl compounds may have the chemicalformula of (CO)₆Co₂(RC≡CR′), wherein R and R′ are independentlyhydrogen, methyl, ethyl, propyl, isopropyl, butyl, tertbutyl, penta,benzyl, aryl, isomers thereof, derivatives thereof, or combinationsthereof. In one example, dicobalt hexacarbonyl butylacetylene (CCTBA,(CO)₆Co₂(HC≡C^(t)Bu)) is the cobalt precursor. Other examples ofdicobalt hexacarbonyl acetyl compounds include dicobalt hexacarbonylmethylbutylacetylene ((CO)₆Co₂(MeC≡C^(t)Bu)), dicobalt hexacarbonylphenylacetylene ((CO)₆Co₂(HC≡CPh)), hexacarbonyl methylphenylacetylene((CO)₆Co₂(MeC≡CPh)), dicobalt hexacarbonyl methylacetylene((CO)₆Co₂(HC≡CMe)), dicobalt hexacarbonyl dimethylacetylene((CO)₆Co₂(MeC≡CMe)), derivatives thereof, complexes thereof, plasmasthereof, or combinations thereof. Other exemplary cobalt carbonylcomplexes include cyclopentadienyl cobalt bis(carbonyl) (CpCo(CO)₂),tricarbonyl allyl cobalt ((CO)₃Co(CH₂CH═CH₂)), or derivatives thereof.

In another embodiment, cobalt amidinates or cobalt amino complexes maybe utilized as cobalt precursors. Cobalt amino complexes have thegeneral chemical formula (RR′N)_(x)Co, where X may be 1, 2, or 3, and Rand R′ are independently hydrogen, methyl, ethyl, propyl, butyl, alkyl,silyl, alkylsilyl, derivatives thereof, or combinations thereof. Someexemplary cobalt amino complexes includebis(di(butyldimethylsilyl)amino) cobalt (((BuMe₂Si)₂N)₂Co),bis(di(ethyldimethylsilyl)amino) cobalt (((EtMe₂Si)₂N)₂Co),bis(di(propyldimethylsilyl)amino) cobalt (((PrMe₂Si)₂N)₂Co),bis(di(trimethylsilyl)amino) cobalt (((Me₃Si)₂N )₂Co),tris(di(trimethylsilyl )amino) cobalt (((Me₃Si)₂N)₃Co), or derivativesthereof.

Some exemplary cobalt precursors include methylcyclopentadienyl cobaltbis(carbonyl) (MeCpCo(CO)₂), ethylcyclopentadienyl cobalt bis(carbonyl)(EtCpCo(CO)₂), pentamethylcyclopentadienyl cobalt bis(carbonyl)(Me₅CpCo(CO)₂), dicobalt octa(carbonyl) (Co₂(CO)₈), nitrosyl cobalttris(carbonyl) ((ON)Co(CO)₃), bis(cyclopentadienyl) cobalt,(cyclopentadienyl) cobalt (cyclohexadienyl), cyclopentadienyl cobalt(1,3-hexadienyl), (cyclobutadienyl) cobalt (cyclopentadienyl),bis(methylcyclopentadienyl) cobalt, (cyclopentadienyl) cobalt(5-methylcyclopentadienyl), bis(ethylene) cobalt(pentamethylcyclopentadienyl), cobalt tetracarbonyl iodide, cobalttetracarbonyl trichlorosilane, carbonyl chloridetris(trimethylphosphine) cobalt, cobalttricarbonyl-hydrotributylphosphine, acetylene dicobalt hexacarbonyl,acetylene dicobalt pentacarbonyl triethylphosphine, derivatives thereof,complexes thereof, plasma thereof, or combinations thereof.

Nitrogen precursors may be used to deposit nitride ornitrogen-containing materials. Nitrogen precursors useful for depositingmaterials as described herein include ammonia (NH₃), hydrazine (N₂H₄),methyl hydrazine ((CH₃)HN₂H₂), dimethyl hydrazine ((CH₃)₂N₂H₂),t-butylhydrazine (C₄H₉N₂H₃), phenylhydrazine (C₆H₅N₂H₃), other hydrazinederivatives, amines, a nitrogen plasma source (e.g., N₂, atomic-N,N₂/H₂, NH₃, or a N₂H₄ plasma), 2,2′-azotertbutane ((CH₃)₆C₂N₂), organicor alkyl azides, such as methylazide (CH₃N₃), ethylazide (C₂H₅N₃),trimethylsilylazide (Me₃SiN₃), inorganic azides (e.g., NaN₃ or CP₂CoN₃)and other suitable nitrogen sources. Radical nitrogen compounds, such asN₃, N₂, N, NH, or NH₂, may be produced by heat, hot-wires, in situplasma, or remote plasma. In one example, the nitrogen precursor isammonia. In another example, the nitrogen precursor contains a nitrogenplasma formed in situ or by a remote plasma system.

Other reactive gases that may be used to deposit various materials,include tantalum nitride, tantalum-containing materials include oxygensources and reductants. A tantalum-containing material, such as tantalumsilicate, tantalum oxide, or tantalum oxynitride may be formed with theaddition of an oxygen source to the vapor deposition (e.g., ALD or CVD)process. Oxygen sources or oxygen precursors include atomic-O, O₂, O₃,H₂O, H₂O₂, organic peroxides, derivatives thereof, or combinationsthereof. Reducing compounds may be included in the vapor depositionprocess to form a tantalum precursor, such as metallic tantalum,tantalum boron nitride or tantalum phosphorous nitride. Reducingcompounds include borane (BH₃), diborane (B₂H₆), alkylboranes (e.g.,Et₃B), phosphine (PH₃), hydrogen (H₂), derivatives thereof, orcombinations thereof.

A detailed description for a processing chamber, such as an ALD chamber,is described in commonly assigned U.S. Pat. No. 6,916,398, and U.S. Ser.No. 10/281,079, filed Oct. 25, 2002, and published as U.S. Pub. No.2003-0121608, which are herein incorporated by reference in theirentirety. In one embodiment, a plasma-enhanced ALD (PE-ALD) process isused to deposit tantalum materials. A chamber and process to performPE-ALD is further described in commonly assigned U.S. Pat. No.6,998,014, which is herein incorporated by reference in its entirety. Adetailed description for a vaporizer or an ampoule to pre-heatprecursors, such as PDMAT or TAIMATA, is described in commonly assignedU.S. Pat. Nos. 6,915,592 and 7,186,385, which are herein incorporated byreference in their entirety. A detailed description for a system todeliver the precursors, such as PDMAT or TAIMATA, to processing chamberis described in commonly assigned U.S. Pat. No. 6,955,211, and U.S. Ser.No. 10/700,328, filed Nov. 3, 2003, and published as U.S. Pub. No.2005-0095859, which are herein incorporated by reference in theirentirety.

Embodiments of the invention provide deposition processes that may beused to deposit materials during a vapor deposition process, such as anALD process. The processes may be used within a variety of vapordeposition processing chambers and gas delivery systems which contain anexpanding channel lid assembly, a converge-diverge lid assembly, amultiple injection lid assembly, or an extended cap lid assembly. Otherembodiments provide methods for depositing materials using these gasdelivery systems during ALD processes.

In one embodiment, the deposition of a layer by ALD will be described inmore detail in reference to the ALD of a tantalum nitride layerutilizing processes as described herein. In one aspect, ALD of atantalum nitride barrier layer includes sequentially providing pulses ofa tantalum precursor and pulses of a nitrogen precursor to theprocessing chamber in which each pulse is separated by a flow of a purgegas and/or chamber evacuation to remove any excess reactants to preventgas phase reactions of the tantalum precursor with the nitrogenprecursor and to remove any reaction by-products. Sequentially providinga tantalum precursor and a nitrogen precursor may result in thealternating absorption of monolayers of a tantalum precursor and ofmonolayers of a nitrogen precursor to form a monolayer of tantalumnitride on a substrate structure for each cycle of pulses. The termsubstrate structure is used to refer to the substrate as well as othermaterial layers formed thereover, such as a dielectric layer.

It is believed that the adsorption processes used to adsorb themonolayer of the reactants, such as the tantalum precursor and thenitrogen precursor, are self-limiting in that only one monolayer may beadsorbed onto the surface of the substrate structure during a givenpulse because the surface of the substrate structure has a finite numberof sites for adsorbing the reactants. Once the finite number of sites isoccupied by the reactants, such as the tantalum precursor or thenitrogen precursor, further absorption of the reactants will be blocked.The cycle may be repeated to a desired thickness of the tantalum nitridelayer.

A continuous flow or a discontinuous flow of a treatment gas, such asDMA, may be introduced into the processing chamber from a gas source orampoule through another valve. The treatment gas may be provided withthe aid of a carrier gas, which includes, but is not limited to, helium,argon, nitrogen (N₂), hydrogen (H₂), or gaseous mixtures thereof. Pulsesof a tantalum precursor, such as PDMAT, may be introduced by a gassource or ampoule through a valve. The tantalum precursor may beprovided with the aid of a carrier gas, which includes, but is notlimited to, helium, argon, nitrogen (N₂), hydrogen (H₂), or gaseousmixtures thereof. Pulses of a nitrogen precursor, such as ammonia, maybe introduced by a gas source through another valve. A carrier gas mayalso be used to help deliver the nitrogen precursor. A purge gas, suchas argon or nitrogen, may be introduced by a gas source through the sameof different valves as for the tantalum and nitrogen precursors.

In one aspect, the flow of purge gas may be continuously provided by thegas source through the valves to act as a purge gas between the pulsesof the tantalum precursor and of the nitrogen precursor and to act as acarrier gas during the pulses of the tantalum precursor and the nitrogenprecursor. In one aspect, delivering a purge gas through two gasconduits provides a more complete purge of the reaction zone rather thana purge gas provided through either one of the gas conduits. In oneaspect, a reactant gas may be delivered through a gas conduit sinceuniformity of flow of a reactant gas, such as a tantalum precursor or anitrogen precursor, is not as critical as uniformity of the purge gasdue to the self-limiting absorption process of the reactants on thesurface of substrate structures. In other embodiments, a purge gas maybe provided in pulses. In other embodiments, a purge gas may be providedin more or less than two gas flows. In other embodiments, a tantalumprecursor gas may be provided in more than a single gas flow (e.g., twoor more gas flows). In other embodiments, a nitrogen precursor gas maybe provided in more than a single gas flow (e.g., two or more gasflows).

The tantalum nitride layer formation is described as starting with theabsorption of a monolayer of a tantalum precursor on the substratefollowed by a monolayer of a nitrogen precursor. Alternatively, thetantalum nitride layer formation may start with the absorption of amonolayer of a nitrogen precursor on the substrate followed by amonolayer of the tantalum precursor. Furthermore, in other embodiments,a pump evacuation alone between pulses of reactant gases may be used toprevent mixing of the reactant gases.

The time duration for each pulse of the tantalum precursor, the timeduration for each pulse of the nitrogen precursor, and the duration ofthe purge gas flow between pulses of the reactants are variable anddepend on the volume capacity of a deposition chamber employed as wellas a vacuum system coupled thereto. For example, (1) a lower chamberpressure of a gas will require a longer pulse time; (2) a lower gas flowrate will require a longer time for chamber pressure to rise andstabilize requiring a longer pulse time; and (3) a large-volume chamberwill take longer to fill, longer for chamber pressure to stabilize thusrequiring a longer pulse time. Similarly, time between each pulse isalso variable and depends on volume capacity of the processing chamberas well as the vacuum system coupled thereto. In general, the timeduration of a pulse of the tantalum precursor or the nitrogen precursorshould be long enough for absorption of a monolayer of the compound. Inone aspect, a pulse of a tantalum precursor may still be in the chamberwhen a pulse of a nitrogen precursor enters. In general, the duration ofthe purge gas and/or pump evacuation should be long enough to preventthe pulses of the tantalum precursor and the nitrogen precursor frommixing together in the reaction zone.

Generally, a pulse time of about 1.0 second or less for a tantalumprecursor and a pulse time of about 1.0 second or less for a nitrogenprecursor are typically sufficient to adsorb alternating monolayers on asubstrate structure. A time of about 1.0 second or less between pulsesof the tantalum precursor and the nitrogen precursor is typicallysufficient for the purge gas, whether a continuous purge gas or a pulseof a purge gas, to prevent the pulses of the tantalum precursor and thenitrogen precursor from mixing together in the reaction zone. Of course,a longer pulse time of the reactants may be used to ensure absorption ofthe tantalum precursor and the nitrogen precursor and a longer timebetween pulses of the reactants may be used to ensure removal of thereaction by-products.

In one example, a processing chamber, a substrate, or a substratesupport may be maintained approximately below a thermal decompositiontemperature of a selected tantalum precursor during an ALD process. Anexemplary heater temperature range to be used with tantalum precursorsidentified herein is approximately between about 20° C. and about 500°C. at a chamber pressure less than about 100 Torr, preferably less than50 Torr. When the tantalum precursor is PDMAT, the heater temperature ispreferably within a range from about 150° C. to about 350° C., morepreferably, from about 250° C. and 300° C., and the internal pressure ofthe processing chamber may be within a range from about 5 Torr to about20 Torr. In other embodiments, it should be understood that othertemperatures and pressures may be used. For example, a temperature abovea thermal decomposition temperature may be used. However, thetemperature should be selected so that more than 50 percent of thedeposition activity is by absorption processes. In another example, atemperature above a thermal decomposition temperature may be used inwhich the amount of decomposition during each precursor deposition islimited so that the growth mode will be similar to an ALD growth mode.

In one example, the processing chamber may be exposed to a treatmentprocess and subsequently, to an ALD process. The process may providepulses of the tantalum precursor gas (e.g., PDMAT in argon) from a gassource or ampoule and having a flow rate within a range from about 100sccm to about 1,000 sccm, preferably, from about 300 sccm to about 700sccm, through an ALD valve having a pulse time of about 1 seconds orless. The process may further provide pulses of the nitrogen precursorgas (e.g., ammonia) may be provided from another gas source at a flowrate within a range from about 20 sccm and about 1,000 sccm, preferably,from about 100 sccm to about 300 sccm, through an ALD valve having apulse time of about 1 second or less. An argon purge gas may have a flowrate within a range from about 1 slm to about 12 slm sccm, preferably,from about 2 slm to about 8 slm, and may be continuously provided fromthe gas source through the valves, as well as through other inlets onthe processing chamber. The time between pulses of the tantalumprecursor and the nitrogen precursor may be about 0.5 seconds or less.

In one embodiment, a tantalum nitride layer may be deposited to asidewall of a via or a similar aperture with a thickness of about 50 Åor less, preferably, about 20 Å or less, and more preferably, about 10 Åor less. A tantalum nitride layer with a thickness of about 10 Å or lessis believed to be a sufficient thickness in the application as a barrierlayer to prevent copper diffusion. In other embodiments, the tantalumnitride layer may have a thickness greater than 50 Å. In one aspect, athin barrier layer containing tantalum nitride deposited by theprocesses described herein may be used in filling submicron (e.g., lessthan 0.15 μm) and smaller features having high aspect ratios (e.g.,greater than 5 to 1).

“Atomic layer deposition” (ALD), as used herein, refers to thesequential introduction of two or more reactive compounds to deposit alayer of material on a substrate surface. The two, three, or morereactive compounds may alternatively be introduced into a reaction zoneor process region of a processing chamber. The reactive compounds may bein a state of gas, plasma, vapor, fluid or other state of matter usefulfor a vapor deposition process. Usually, each reactive compound isseparated by a time delay to allow each compound to adhere and/or reacton the substrate surface. In one aspect, a first precursor or compound Ais pulsed into the reaction zone followed by a first time delay. Next, asecond precursor or compound B is pulsed into the reaction zone followedby a second delay. Compound A and compound B react to form a depositedmaterial. During each time delay a purge gas is introduced into theprocessing chamber to purge the reaction zone or otherwise remove anyresidual reactive compound or by-products from the reaction zone.Alternatively, the purge gas may flow continuously throughout thedeposition process so that only the purge gas flows during the timedelay between pulses of reactive compounds. The reactive compounds arealternatively pulsed until a desired film thickness of the depositedmaterial is formed on the substrate surface. In either scenario, the ALDprocess of pulsing compound A, purge gas, pulsing compound B and purgegas is a cycle. A cycle can start with either compound A or compound Band continue the respective order of the cycle until achieving a filmwith the desired thickness. In an alternative embodiment, a firstprecursor containing compound A, a second precursor containing compoundB and a third precursor containing compound C are each separately pulsedinto the processing chamber. Alternatively, a pulse of a first precursormay overlap in time with a pulse of a second precursor while a pulse ofa third precursor does not overlap in time with either pulse of thefirst and second precursors. “Process gas” as used herein refers to asingle gas, multiple gases, a gas containing a plasma, combinations ofgas(es) and/or plasma(s). A process gas may contain at least onereactive compound for a vapor deposition process. The reactive compoundsmay be in a state of gas, plasma, vapor, fluid, or other state of matteruseful for a vapor deposition process. Also, a process gas may contain apurge gas or a carrier gas and not contain a reactive compound.

“Substrate” or “substrate surface,” as used herein, refers to anysubstrate or material surface formed on a substrate upon which filmprocessing is performed. For example, a substrate surface on whichprocessing can be performed include materials such as silicon, siliconoxide, strained silicon, silicon on insulator (SOI), carbon dopedsilicon oxides, silicon nitride, doped silicon, germanium, galliumarsenide, glass, sapphire, quartz, and any other materials such asmetals, metal nitrides, metal alloys, and other conductive materials,depending on the application. Barrier layers, metals or metal nitrideson a substrate surface may include titanium, titanium nitride, titaniumsilicide nitride, tungsten, tungsten nitride, tungsten silicide nitride,tantalum, tantalum nitride, or tantalum silicide nitride. Substrates mayhave various dimensions, such as 200 mm or 300 mm diameter wafers, aswell as, rectangular or square panes. Substrates include semiconductorsubstrates, display substrates (e.g., LCD), solar panel substrates, andother types of substrates. Unless otherwise noted, embodiments andexamples described herein may be conducted on substrates with a 200 mmdiameter or a 300 mm diameter. Substrates on which embodiments of theinvention may be useful include, but are not limited to semiconductorwafers, such as crystalline silicon (e.g., Si<100> or Si<111>), siliconoxide, glass, quartz, strained silicon, silicon germanium, doped orundoped polysilicon, doped or undoped silicon wafers and patterned ornon-patterned wafers. Substrates may be exposed to a treatment processto polish, etch, reduce, oxidize, hydroxylate, anneal, and/or heat thesubstrate surface.

Although the invention has been described in terms of specificembodiments, one skilled in the art will recognize that various changesto the reaction conditions, e.g., temperature, pressure, film thicknessand the like can be substituted and are meant to be included herein andsequence of gases being deposited. For example, sequential depositionprocess may have different initial sequence. The initial sequence mayinclude exposing the substrate to the nitrogen precursor gas before thetantalum precursor gas is introduced into the processing chamber. Inaddition, the tantalum nitride layer may be employed for other featuresof circuits in addition to functioning as a diffusion barrier forcontacts. Therefore, the scope of the invention should not be based uponthe foregoing description. Rather, the scope of the invention should bedetermined based upon the claims recited herein, including the fullscope of equivalents thereof.

While the foregoing is directed to embodiments of the invention, otherand further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. A method for depositing a material on a substrate surface, comprising: exposing a substrate sequentially to an alkylamino metal precursor gas and a second precursor gas while depositing a material on the substrate during an atomic layer deposition process; and exposing the substrate to a treatment gas comprising an alkylamine compound prior to or during the atomic layer deposition process.
 2. The method of claim 1, wherein the substrate is continuously exposed to the treatment gas during the atomic layer deposition process.
 3. The method of claim 1, wherein the substrate is periodically exposed to the treatment gas during the atomic layer deposition process.
 4. The method of claim 1, wherein the substrate is exposed to the treatment gas prior to the atomic layer deposition process.
 5. The method of claim 1, wherein the exposing the substrate to the treatment gas reduces the deposition rate of the material during the atomic layer deposition process by about 95% or less.
 6. The method of claim 1, wherein the material is deposited on the substrate at a deposition rate within a range from about 0.05 Å/cycle to about 1.0 Å/cycle.
 7. The method of claim 6, wherein the deposition rate is about 0.5 Å/cycle.
 8. The method of claim 1, wherein the alkylamine compound has the chemical formula of H₂NR or HNR′R″, where each R, R′, and R″ is independently selected from the group consisting of methyl, ethyl, propyl, butyl, amyl, phenyl, aryl, isomers thereof, derivatives thereof, and combinations thereof.
 9. The method of claim 8, wherein the alkylamine compound is selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, methylethylamine, propylamine, dipropylamine, butylamine, dibutylamine, isomers thereof, derivatives thereof, and combinations thereof.
 10. The method of claim 1, wherein the alkylamino metal precursor gas comprises a tantalum precursor selected from the group consisting of pentakis(dimethylamino) tantalum, pentakis(diethylamino) tantalum, pentakis(ethylmethylamino) tantalum, tert-butylimino tris(dimethylamino) tantalum, tert-butylimino tris(diethylamino) tantalum, tert-butylimino tris(ethylmethylamino) tantalum, tert-amylimino-tris(dimethylamino) tantalum, tert-amylimino-tris(diethylamino) tantalum, tert-amylimino-tris(ethylmethylamino) tantalum, and derivatives thereof.
 11. The method of claim 10, wherein the tantalum precursor is pentakis(dimethylamino) tantalum and the alkylamine compound gas comprises methylamine or dimethylamine.
 12. The method of claim 10, wherein the second precursor gas comprises a nitrogen precursor and the material deposited comprises tantalum nitride.
 13. The method of claim 12, wherein the nitrogen precursor comprises ammonia.
 14. The method of claim 1, wherein the treatment gas further comprises at least one carrier gas selected from the group consisting of ammonia, hydrogen, nitrogen, argon, helium, and combinations thereof.
 15. The method of claim 14, wherein the treatment gas comprises dimethylamine, ammonia, and argon.
 16. A method for depositing a material on a substrate surface, comprising: exposing a substrate sequentially to an alkylamino metal precursor gas and a second precursor gas while depositing a material on the substrate at a first deposition rate during an atomic layer deposition process within a processing chamber; exposing the substrate to a treatment gas comprising an alkylamine compound prior to or during the atomic layer deposition process; and depositing the material on the substrate at a second deposition rate during the atomic layer deposition process, wherein the second deposition rate is less than the first deposition rate.
 17. The method of claim 16, wherein the second deposition rate is about 95% or less of the first deposition rate.
 18. The method of claim 16, wherein the second deposition rate is within a range from about 0.05 Å/cycle to about 1.0 Å/cycle.
 19. The method of claim 18, wherein the second deposition rate is about 0.5 Å/cycle.
 20. The method of claim 16, wherein the alkylamino metal precursor gas comprises a tantalum precursor selected from the group consisting of pentakis(dimethylamino) tantalum, pentakis(diethylamino) tantalum, pentakis(ethylmethylamino) tantalum, tert-butylimino tris(dimethylamino) tantalum, tert-butylimino tris(diethylamino) tantalum, tert-butylimino tris(ethylmethylamino) tantalum, tert-amylimino-tris(dimethylamino) tantalum, tert-amylimino-tris(diethylamino) tantalum, tert-amylimino-tris(ethylmethylamino) tantalum, and derivatives thereof.
 21. The method of claim 20, wherein the tantalum precursor is pentakis(dimethylamino) tantalum and the alkylamine compound gas comprises methylamine or dimethylamine.
 22. The method of claim 20, wherein the second precursor gas comprises ammonia and the material deposited comprises tantalum nitride.
 23. The method of claim 16, wherein the treatment gas comprises dimethylamine, ammonia, and argon.
 24. A method for depositing a material on a substrate surface, comprising: exposing a substrate disposed within the processing chamber to a carrier gas having a continuous flow; exposing the substrate sequentially to a tantalum precursor gas and a nitrogen precursor gas while depositing a tantalum nitride material on the substrate during an atomic layer deposition process, wherein the tantalum precursor gas comprises pentakis(dimethylamino) tantalum, and the atomic layer deposition process comprises sequentially pulsing the tantalum precursor gas and the nitrogen precursor gas into the carrier gas with the continuous flow to deposit the tantalum nitride material; and introducing a treatment gas comprising dimethylamine to the carrier gas to expose the substrate to the treatment gas prior to or during the atomic layer deposition process.
 25. The method of claim 24, wherein the exposing the substrate to the treatment gas reduces the deposition rate of the material during the atomic layer deposition process by about 95% or less. 